Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F14/02—Monomers containing chlorine
  • C08F14/04—Monomers containing two carbon atoms
  • C08F14/08—Vinylidene chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/02—Monomers containing chlorine
  • C08F214/04—Monomers containing two carbon atoms
  • C08F214/08—Vinylidene chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
  • C08F214/22—Vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
  • C08F214/22—Vinylidene fluoride
  • C08F214/225—Vinylidene fluoride with non-fluorinated comonomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08L27/08—Homopolymers or copolymers of vinylidene chloride
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2438/00—Living radical polymerisation
  • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

• the present invention relates to the field of polymerizations involving monomers in a liquid phase dispersed in a continuous liquid phase (dispersed phase polymerization), including in particular emulsion polymerizations. More specifically, the invention relates to polymerizations of this type using particular dispersed phase stabilizers, so-called "reactive stabilizers”.
• the reactive stabilizer used in these reactions is a molecule that allows one hand to stabilize the droplets of the dispersed phase containing the monomers and which is further suitable to be engaged in the polymerization reaction.
• Such reactive stabilizers have, among others, the advantage of substituting all or part of the additional surfactants that it is otherwise necessary to implement to stabilize the dispersed phase and they lead thereby to dispersions of polymers (latex ) interesting in that they are free of such surfactants or at least in that they have a reduced content of such reagents.
• ATRP type atom transfer radical polymerization
• NMP nitroxide-mediated polymerization
• RAFT or MADIX RAFT or MADIX
• reactive stabilizers ensure, on the one hand, the stabilization of the emulsion of the droplets of the dispersed phase because of their hydrophilic nature, and on the other hand they act as a control agent for the polymerization, typically by reversible transfer by addition-fragmentation, whereby the polymer chains grow from this control agent by progressive consumption of the monomers contained in each droplet, according to a process well known per se, where the polymer chains present a so-called "living" character, in the sense that each step of incorporating a monomer unit into the chain leads to a polymer which remains carrying a reactivable chain end for the subsequent incorporation of another monomeric unit according to the same addition-fragmentation process (for more details concerning the controlled or "living" radical polymerization and the obtaining of chains growing from the transfer agent, one can notably refer to Handbook of RAFT polymerization, Ed.
• An object of the present invention is to provide a dispersed phase polymerization process adapted to the implementation of a large number of hydrophobic monomers and in particular adapted to the dispersed phase polymerization of hydrophobic N-vinyl monomers.
• the inventors have demonstrated the interest of implementing a new type of reactive stabilizer, namely a living polymer chain resulting from a controlled radical polymerization RAFT or MADIX of N- (vinyl monomers). lactam).
• the inventors have demonstrated a method for preparing a polymer comprising a dispersed phase polymerization step in the presence of a reactive stabilizer, in which is placed in the presence of an aqueous phase:
• At least one ethylenically unsaturated monomer generally in the dispersed state; at least one source of free radicals;
• each of R b and R c represents, independently:
• alkyl group preferably chlorinated and / or fluorinated, more preferably perchlorinated or perfluorinated.
• reactive stabilizers containing a thiocarbonylthio group -S (C S) - analogous to those of the present invention.
• invention which contain a polymer chain other than a chain comprising monomer units (N-vinyl lactam), or a chain comprising less than 50%, or even less than 30% monomer units (N-vinyl lactam).
• each of R b and R c represents, independently:
• step (E1) comprising a step (E1), wherein these monomers are introduced into an aqueous phase, generally in the dispersed state, together with
• SR2 reactive stabilizer
• SR2 at least one reactive stabilizer, hereinafter referred to as "SR2"
• hydrophilic monomers of acrylate type for example acrylic acid and its salts, such as sodium acrylate, as well as esters of water-soluble acrylic acid, such as, for example, 2-hydroxyethyl acrylate or oligo or polyethylene glycol acrylates.
• hydrophilic monomers of acrylamido type such as, for example, acrylamide, dimethylacrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid and its salts, acrylamidopropyltrimethylammonium chloride (APTAC), dimethylaminopropylacrylamide, NN-diethylacrylamide N-isopropyl acrylamide, N-morpholine acrylamide, N-hydroxy ethyl acrylamide.
• acrylamido type such as, for example, acrylamide, dimethylacrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid and its salts, acrylamidopropyltrimethylammonium chloride (APTAC), dimethylaminopropylacrylamide, NN-diethylacrylamide N-isopropyl acrylamide, N-morpholine acrylamide, N-hydroxy ethyl acrylamide.
• ATAC acrylamidopropyltrimethylam
• hydrophilic monomers of the methacrylate type for example methacrylic acid and its salts, such as sodium methacrylate and also oligo or polyethylene glycol methacrylate, 3- [N- (3-propyl methacrylate) -N, N- dimethyl] ammoniopropane sulfonate), hydroxyethyl methacrylate.
• methacrylic acid and its salts such as sodium methacrylate and also oligo or polyethylene glycol methacrylate, 3- [N- (3-propyl methacrylate) -N, N- dimethyl] ammoniopropane sulfonate), hydroxyethyl methacrylate.
• hydrophilic monomers of methacrylamido type such as, for example, methacrylamide, 3- [N- (3-methacrylamidopropyl) -N, N-dimethyl] ammoniopropane sulphonate)) (SPP), [(3-methacrylamidopropyl) -N, N-trimethyl) ammonium chloride (MAPTAC).
• methacrylamido type such as, for example, methacrylamide, 3- [N- (3-methacrylamidopropyl) -N, N-dimethyl] ammoniopropane sulphonate) (SPP), [(3-methacrylamidopropyl) -N, N-trimethyl) ammonium chloride (MAPTAC).
• vinyl-type hydrophilic monomers for example vinyl phosphonic acid, sodium vinyl sulphonate, 2-vinyl pyridine, 4-vinyl pyridine, and quaternized versions and vinyl imidazole
• hydrophilic monomers of the allyl type for example diallyldimethylammonium chloride (DADMAC) or dimethylammoniummethyl phosphonate diallyl (DALP).
• DMDMAC diallyldimethylammonium chloride
• DALP dimethylammoniummethyl phosphonate diallyl
• the polymer chain comprising non-N-vinyl lactam monomer units may optionally comprise monomeric units (N-vinyl lactam), in a proportion of less than 50%, or even less than 30%.
• halogenated monomers of the above-mentioned type involves the addition of halogenated surfactants, most often fluorinated, such as fluoroamphipiles of the type of ammonium salts of perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) or perfluorononanoic acid (PFNA) whose use is increasingly controversial because of their toxicological profile (toxicity associated with persistence).
• fluorinated such as fluoroamphipiles of the type of ammonium salts of perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) or perfluorononanoic acid (PFNA) whose use is increasingly controversial because of their toxicological profile (toxicity associated with persistence).
• the invention makes it possible to provide fluorinated latices in which the surfactants of this type are substituted at least in part, preferably entirely, by reactive stabilizers according to the invention.
• the reactive stabilizers employed may be halogenated or fluorinated (for example, reactive stabilizers bearing fluorinated or chlorinated groups may be used) but, contrary to the usual methods for dispersed phase polymerization, the process of the invention, which employs reactive stabilizers, leads to an immobilization of the stabilizers on the polymer particles, and therefore does not lead to the surfactant release effects that can be observed with the usual fluorinated latices.
• the invention therefore authorizes in this context the use of fluorinated stabilizers with reduced impacts in terms of toxicity.
• the method of the invention provides access to a controlled polymerization of the aforementioned monomers particularly effective and unprecedented halogenated monomers.
• the source of free radicals employed in step (E1) is preferably a redox polymerization initiator. More generally, it may be any initiator capable of generating free radicals under the conditions of step (E1), preferably at a temperature below 40 ° C., more advantageously at a temperature of less than or equal to 30 ° C. vs.
• the polymerization in dispersed phase carried out in the context of the invention is, in general, a polymerization which leads, at the end of reaction to an emulsion or a dispersion of the polymer synthesized in the aqueous phase.
• the monomers can typically be used in the dispersed state within the aqueous phase (emulsion polymerization, for example).
• the monomers may be employed without the formation of a monomer dispersion in the aqueous phase.
• the polymer precipitates gradually and disperses in the form of the particles (dispersion polymerization, typically).
• the monomers can be introduced gradually during the polymerization by permanently maintaining a concentration of said monomers below their solubility limit.
• the monomers can be introduced continuously or semi-continuously into an aqueous phase initially containing only a portion of the monomers at an initial concentration lower than the solubility limit.
• the reactive stabilizer used according to the invention can stabilize the emulsion or the polymer dispersion obtained at the end of the reaction. In some embodiments (emulsion polymerization, in particular), it can also stabilize the initial dispersion of monomers.
• the reactive stabilizer employed in step (E1) is typically a polymer resulting from a step (E0) of controlled radical polymerization of a composition comprising:
• an initiator of radical polymerization which is typically a redox system.
• the initiator of the radical polymerization employed may be a thermal system.
• the work that has been done by the inventors on this subject has now made it possible to demonstrate that it is possible to carry out a radical polymerization both in an aqueous medium and in an effectively controlled manner, provided that this reaction is initiated. radical through a redox system.
• the reactive stabilizer employed in step (E1) is prepared in organic solvent medium or without solvent. If necessary, it is replaced in water prior to step (E1).
• step (E1) stable polymer dispersions (latex) are generally obtained with polymer particles which have a controlled mass and size, which constitutes another particular object of the present invention.
• the invention may in particular give access to fluorinated polyolefin latices (especially fluorinated vinyl polymers) free of fluorinated surfactants or at least having a level of surfactant well below those commonly used.
• step (E1) may be used alone or in combination with other stabilizers.
• step (E1) is conducted in the absence of other stabilizing agents, especially in the absence of surfactants.
• step (E1) can be carried out by implementing the reagent stabilizing agents of the invention with other co-stabilizers, for example surfactants.
• the reactive stabilizer employed in step (E1) may typically be employed at a mass concentration of from 0.01% to 50%.
• the polymer / stabilizer mass ratio which remains generally greater than 0.005, preferably greater than 0.01, for example greater than 0.02, in particular to ensure a sufficient stabilizing effect.
• This weight ratio polymer / stabilizer generally need not be greater than 400, and it is typically less than or equal to 100, or even less than or equal to 50. Thus, this ratio may especially be between 0.005 and 400, for example 0.05 and 300, especially between 0.02 and 50.
• control agent employed in the controlled radical polymerization implemented in step (E0) which is typically a RAFT or MADIX control agent.
• this control agent used in step (E0) may carry several thiocarbonylthio groups.
• the groups or Z when substituted, may be substituted with optionally substituted phenyl groups, optionally substituted aromatic groups, saturated or unsaturated carbon rings, saturated or unsaturated heterocycles, or alkoxycarbonyl or aryloxycarbonyl groups (- COOR), carboxy (-COOH), acyloxy (-O2CR), carbamoyl (-CONR2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH) , amino (-NR2), halogen, perfluoroalkyl C n F 2n + 1, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as the alkaline salts of carboxylic acids, alkali metal salts of s
• R 1 is a substituted or unsubstituted alkyl group, preferably substituted.
• the optionally substituted alkyl, acyl, aryl, aralkyl or alkyne groups to which reference is made in the present description generally have 1 to 20 carbon atoms, preferably 1 to 12, and more preferably 1 to 9 carbon atoms. They can be linear or branched. They may also be substituted by oxygen atoms, in particular esters, sulfur or nitrogen atoms.
• alkyl radicals mention may especially be made of the methyl, ethyl, propyl, butyl, pentyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, decyl or dodecyl radical.
• alkynes in the sense of the present description are radicals generally of 2 to 10 carbon atoms, they have at least one acetylenic unsaturation, such as the acetylenyl radical.
• acyl groups within the meaning of the present description are radicals generally having from 1 to 20 carbon atoms with a carbonyl group.
• aryl radicals that may be used according to the invention, mention may in particular be made of the phenyl radical, optionally substituted in particular by a nitro or hydroxyl function.
• aralkyl radicals mention may especially be made of the benzyl or phenethyl radical, optionally substituted in particular by a nitro or hydroxyl function.
• this polymer chain may be derived from a radical or ionic polymerization or from a polycondensation. In the context of the present invention, it is particularly advantageous to use as control agents xanthates, dithiocarbamates, or dithiocarbazates.
• xanthate compounds such as for example 0-ethyl-S- (1-methoxycarbonylethyl) xanthate of formula (CH 3 CH (CO 2 CH 3)) are used as the control agent in step (E0).
• a control agent well adapted to the implementation of step (E0) is the compound marketed by Rhodia under the name Rhodixan A1.
• the sources of free radicals employed in steps (E0) and (E1) may be the same or different, and they are typically the same for practical reasons.
• a free radical source suitable both in the step (E0) and in the step (E1) is a redox polymerization initiator which comprises two agents, namely an oxidizing agent and a reducing agent, which can be introduced simultaneously or consecutively.
• the reducing and oxidizing agents are introduced separately, which makes it possible to delay initiation of the polymerization until the introduction of the second agent.
• a step employing such a redox agent is carried out (i) by first forming a mixture comprising one of the oxidizing or reducing agents mixed with the monomers and the control agent (which is the reactive transfer agent in step (E1)), then (ii) adding to this mixture the other agent (respectively reducing or oxidizing).
• the advantageous effects demonstrated by the inventors in the context of the present invention are, in general, all the more marked that the difference between the standard redox potentials of the oxidant and the reducing agent (E ox -E red ) is important. .
• the difference between the standard redox potentials of the oxidizing agent and the reducing agent (E ox -E red ) is between 1 and 2 V. Furthermore, it can be interesting that the standard redox oxidation potential E ox of the oxidizing agent (Ox) used in step (E0) is lower (preferably at least 0.2 V, more preferably at least 0, 5 V, or at least 1V) to that of the monomers employed.
• oxidizing agents in this context are hydroperoxides, especially tert-butyl peroxide (t-BuOOH). Hydrogen peroxide is another possible oxidizing agent.
• the agents present in the redox system do not contain acids likely to induce parasitic reactions of the monomers suitable for leading to undesired byproducts, and more generally that they do not contain compounds with a sufficiently low pKa to induce such reactions.
• reducing agents (Red) and oxidizing agents (Ox) having a pKa greater than 4, more preferably greater than 6, or even 6.5, and preferably at least 7 , which allows the rate of by-products to be reduced, generally to at most a few% in the synthesized polymer.
• Redox systems well suited to the implementation of steps (E0) and (E1) of the process of the invention comprise tert-butyl peroxide (t-BuOOH) as an oxidizing agent, combined with a reducing agent. selected from ascorbic acid or sodium sulfite.
• a reducing agent selected from ascorbic acid or sodium sulfite.
• the tert-butyl hydroperoxide / sodium sulfite redox system is particularly interesting.
• the use of this system in step (E0) allows to polymerize at room temperature and in water with a very low level of by-products, typically remaining well below 5%.
• steps (E0) and (E1) Given the implementation of the redox system in step (E0), this step is advantageously carried out in an aqueous medium, typically using water as a feedstock. single solvent. It thus makes it possible to obtain a polymer directly in an aqueous medium without having to use organic solvents, which makes the process particularly suitable for use on an industrial scale. Furthermore, the steps (E0) and (E1) are advantageously carried out at low temperature, preferably below 40 ° C, more preferably at a temperature of less than or equal to 30 ° C, especially between 5 and 25 ° C . These two steps can therefore be performed for example at room temperature, which is another advantage of the method of the invention, in terms of energy costs.
• the polymer blocks prepared in steps (E0) and (E1) may be homopolymers or random copolymers (or gradient, especially in step (E0)).
• vinyl chloride H 2 C CHCl (VC)
• These monomers may be homopolymerized or copolymerized in step (E1), with each other, or with other ethylenically unsaturated monomers, halogenated or not (typically less than 50 mol% of non-halogenated monomer, if appropriate).
• step (E1) provides access to polymer dispersions.
• it is a latex comprising dispersed particles formed of block polymers derived from the controlled radical polymerization such as obtained at the end of step (E1) which contain dispersed particles formed of block polymers resulting from the polymerization radical controlled conducted in this step, each of these block polymers comprising:
• a first block generally hydrophilic, or optionally amphiphilic, corresponding to the polymer chain of the reactive stabilizers employed in step (E1);
• a second block, hydrophobic comprising a polymer chain resulting from the polymerization of the ethylenically unsaturated monomers employed in step (E1), generally terminated by the thiocarbonylthio reactive group (xanthate for example) initially present on the reactive stabilizer used in step (E1)
• step (E1) Given the conditions of implementation of step (E1), the block polymers resulting from this step schematically combine within each particle to form a "core" of particle based hydrophobic blocks and a External "shell” based on the polymer chains initially present on the reactive stabilizer, covalently bound to the chains of the heart.
• the latexes thus obtained have the advantage of being stable without requiring the presence of surfactants.
• an additional surfactant is not excluded, it is most often interesting that no additional surfactant is implemented in step (E1) or subsequent thereto. which makes it possible to obtain latexes that are free of surfactants.
• Immobilization of the stabilizing agent on the particle by covalent grafting which is intrinsic to the implementation of step (E1), contributes to the stabilization of the latex, by inhibiting the desorption phenomena observed when using conventional surfactants instead of reactive stabilizers of the invention.
• step (E1) makes it possible to obtain a controlled surface chemistry on the surface of the latex particles, which can be modulated according to the nature of the polymer chain of reactive stabilizers on which reactive groups can to be introduced:
• step (E1) in particular by introducing monomers, functionalized or not, in step (E0); and or
• step (E1) for example by grafting reaction via groups present on the polymer chains immobilized on the surface of the particles of the latex.
• step (E1) also allows extremely fine control of the number-average molecular weight Mn of the synthesized polymers, in a very simple and straightforward manner. Therefore, the step (E1) allows a very easy fine control of the size of the formed particles, which can be used in particular to optimize the colloidal stability.
• polymer particles are obtained which tend, in the same way to have homogeneous diameters and tightened around a mean value.
• the polymers obtained according to step (E1) in the form of particles have a living character and can therefore, in absolute terms, be used as living polymers for the subsequent synthesis of block copolymers on which a third block will be grafted.
• the polymers obtained in step (E1) can be used as control agents in a polymerization step subsequent to step (E1).
• step (E1) it may be desirable to deactivate the reactive end of the polymers obtained in the outcome of step (E1). This deactivation can be performed after step (E1), or it can complete this step (for example, it can be implemented when the desired molecular weight or particle size of the expected latex is reached).
• the method then comprises, after step (E1), a step (E2) chemical treatment of the chain end.
• the reactive stabilizer employed in step (E1) is a xanthate
• the latexes obtained at the end of step (E1) can be used in a very large number of applications, in particular for the production of paints, coatings and adhesives, for the preparation of building materials, or even in cosmetic or body care compositions, in phytosanitary formulations or intended for the field of agriculture or even in fluids for petroleum extraction.
• the polymer dispersion resulting from step (E1) which comprises block polymers resulting from controlled radical polymerization as obtained at the end of step (E1), organized in the form of micelles, usable as a polymerization site for controlled radical polymerizations.
• reaction mixture was cooled to 10 ° C. and degassed by a slight bubbling of pure nitrogen for 5 minutes with stirring (magnetic bar). Then, 0.26 g of sodium sulfite was added at once under a stream of nitrogen. The reaction mixture was left stirring for 3 hours at 10 ° C (+/- 5 ° C).
• Static light scattering analysis (Malvern Zetasizer) provides Dz particle size values of 241 nm and a particle polydispersity of 0.04.
• reaction mixture was cooled to 10 ° C. and degassed by a slight bubbling of pure nitrogen for 5 minutes with stirring (magnetic bar). Then, 0.26 g of sodium sulfite was added at once under a stream of nitrogen.
• Static light scattering analysis (Malvern Zetasizer) provides 195 nm Dz particle size values and 0.03 particle polydispersity.

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